Pressure molded cement products and methods for producing same



M 7 c United States Patent Officehto, ,793,13: //r

Patented May 21, 1957 The following are representative of formualtions which 2 793 130 may be applied to glass fibers for protection against destruction during pressure molding of cementitious ma- PRESSURE MOLDED CEMENT PRODUCTS AND terials:

METHODS FOR PRODUCING SAME 5 Example 1 Richard F. Shannon, Lancaster, and Robert H. Mitchell, P t par ially dcxlriniud starch New Concord, Ohio, assignors to Owens-Coming Fiber- 2.0 percent hydrogenated vegetable oil glas Corporation, a corporation of Delaware 0.3 percent non-ionic emulsifying agent (polyglycol esters of fatty acids) No f?: "f 1953 m 0.6 percent cationic softener (tetraethylene pentamine stearic acid condensate solubilized with acetic acid) 9 Claims. (Cl. l06--99) 89.1 percent water Example 2 This invention relates to the manufacture of products P P y y 396m? Plasticiled with 2040 P formed of Portland cement and other cementitious macen ibutyl phthalate terials reinfor'd ce with "1' s and it is an object of 2- p t metbacrylate chmmic chloride this invention to produce and to provide a method for 0.4 percent pelargonate amide solubilized with acetic acid producling -glass fiber reinforced cementitious products P r n a r having improved physical and mechanical properties such Example 3 gi sgfzi g ggf and denslty and higher and Synthetic A49 alkyd, manufactured by Hercules Powder Glass fibers have been embodied as agents for rein- Company of Y f forcement and improvement in flexure strength of ce- These composltlons y be pp to the 81855 fiber menfitioug composifigns, as describgd in the appending surfaces as a size in COl'lillIlCiiOl'l With the operation for applications Ser, N 223,660, fil d April 28, 1951, forming the fibers by rapid attenuation of molten streams titled Reinforced Inorganic Molded Products, now of glass, as described in Biefeld Patent No. 2,392,805, or U. 8. Patent No. 2,781,274; Ser. No. 284,201, filed by other conventional coating means. The amount present April 24, 1952, entitled Plastic Molding Composition," on the surfaces is not critical as long as the glass fiber now U. S. Patent No. 2,770,840; Ser. No. 284,202, filed surfaces are covered substantially throughout their lengths. April 24, 1952, entitled Plastic Molding Composition, When the glass fibers have been pretreated in the mannow abandoned, and Sen No, 200,077, filed Decemner described to embody a cushioning agent for protectber 9, 1950, entitled Fibrous Board and Method of ing the glass fibers against destruction by abrasion when Making the Same, w U S, Pat t N 2,664,606, molded with cementitious materials, pressure molding but fabrication of glass fibers into finished cementitious ca or t e fi t time, be used successfully to pr products has been limited chiefly to processes wherein dense cementitious products reinforced with glass fibers little, if any, pressure is employed in forming. This is to provide a marked improvement in strength and flexure. because the sharp cement particles of the cement and, Where before aloss in strength resulted when cementitious apparently, the glass fibers themselves causes disintecompositions reinforced with glass fibers were molded gration of the glass fibers under molding pressure. As under pressure, ma kedimprovements in strength are a result insufiicient glass fibers of reinforcing length rcsecured when the g assfibers have been pretreated in acmain in the molded product and the expected improvecordance with the practice 0 l5 invention. Where ments in strength properties and fiexure are seldom, if before little improvemEnt-irr'strcnglh resulted from the ever, achieved. In fact the strength properties remain pressure molding of cementitious materials, when glass at the level secured in the absence of glass fiber in the fibers treated in accordance with the practice of this incementitious product. vention are incorporated in an equivalent cementitious It is an object of this invention to provide a method composition, products molded under pressure have been for achieving improvement in strength from the prgssure found to have strength properties increased four times molding of glass fiberreipforced cementitious products over that secured without pressure and many more times and it IS a relaied ob ect to provide means for preventover that secured by pressure molding with untreated glass ing the disintegration of the glass fibers res re fibers present as a reinforcement.

molding wbcn-prescfltffl' h'e fig'nibiif" slurry. To the present, the conditions responsible for this It has been found tha disintegration and damage of marked improvement in strength and fiexure resulting the glass fibers when molded under pressure in comfrom pressure molding of glass fiber reinforced cementibination with cementitious compositions can be alleviated tious compositions has not been determined. Since coma great extent if th e gl3 rss ,fihc surfacs ar coated with parable results have not been secured merely by the addia material which impair -r 0 protion of such organic g oating compositions .orJssinous.

The desired cushionin rats-n which coating materiaTs'a j'pgredicntsinthe cmfin slurry, it enables molding of glass fiber reinforced cementitious rs believed that the improvements in strength flows more compositions at pressures as high as 2000 pounds per directly from the compressive forces which bring about square inch without excessive damage has been achieved more intimate contact between the cement particles themwhen the glass fiber surfaces are coated in advance of selves and between the cement particles and the glass molding with organic sizes formulated of such materials fibers and also because of the greater number of such as dextrinized starch, gelatin, casein, carbohydrates, and points of contact forced between the cement particles and ther colloids, or geirrgup maldehlusins, urea 5 the glass fibers whereby greater utilization is made of the formaldehyde resins, me amine vformaldehyde resins, polyhigh strength properties of the glass fibers present.

- est'e'r resins and the like thermosetting materials or poly- While the organic coatings on the glass fiber surfaces t acrylates and the like thermoplastic resins, in solappear to impart sufficient cushioning action to protect the vent solution or in aqueous emulsion, and without but a: glass fibers from damage and destruction thereby, for the preferably with lubricants such as vegetable and minfirst time, to permit the successful use of high pressure in i eral oils, sulf oils, fatty acids, fatty acid esters and molding cementitious compositions, the organic materials the like, an which also contain wetting agents. on the glass fiber surfaces are incapable of developing an adequate bonding relation with the highly hydrophilic surfaces of the glass fibers and are therefore incapable of providing maximum utilization of the high strength of the glass fibers for reinforcement of the cementitious products. Although increased strength is secured, to an extent, by increasing the concentration of fibers, the amount of glass fibers of reinforcing lengths (/4-4 inches) which can be incorporated into a slurry without destroying the plastic flow necessary for molding limited, usually to a maximum of about 8-12 percent. Very often only percent or less glass fibers on the weight basis can be incorporated before the-cement slurry becomes too stitf to handle.

Thus it is another object of this invention to produce treated glass fibers and to provide a method for producing same in advance of their combination with cements to protect the glass fibers from destruction in response to molding under pressure and also to im rove the bondin relation between the glass fibers and Mimi iertals with which the glass fibers are combined for molding into products, with or without ressure, to enable more complete utilizmsfifflrproperties of the glass fibers incorporated as a reinforcement and flexibilizing agent and it is a related object to produce new and improved glass fiber reinforced cementitious products embodying same.

In accordance with the further practice of this invention, the desired improvement in the bonding relation between the glass fiber surfaces and the cementitious materials and the desired cushioning action to minimize destruction of the glass fibers during molding under pressure is achieved by the treatment of the glass fibers to form an inorganic coating in situ on the glass fiber surfaces by reaction of a polyvalent metal salt and a water soluble oxide or hydroxide to form an insoluble reaction product, probably the corresponding polyvalent metal hydroxide, which functions both as an anchoring and as a cushioning agent.

The following will demonstrate the practice of this invention:

Example 4 Upon attenuation of the glass fiber filaments from molten streams of glass, as by the process described in the Biefeld Patent No. 2,392,805, the filaments of glass fibers are coated in forming with a 3 percent aqueous solution of aluminum chloride. Soon thereafter, and preferably while the fibers are still wet with the solution of the aluminum chloride, the surface is wet with a 1 percent solution of ammonium hydroxide. A reaction product immediately develops in the form of a water insoluble gelatinous coating which is believed to be a form of aluminum hydroxide. The reaction product remains strongly bonded to the glass fiber surfaces. While elevated temperatures, such as up to 300-350 F. may be used to accelerate drying, it will be sufiicient if glass fibers with the reaction product formed in situ as a coating on the surfaces thereof are allowed to dry slowly in air. The glass fibers having the reaction product on the surface are able to resist destruc ion an when present in cementitious compositions molded under pressure and the reaction product formed in situ on the glass fiber surfaces functions excellently as an anchoring agent strongly to bond the cement particles to the glass fiber surfaces.

. Instead of carrying out the described treatments to form the reaction product in situ on glass fibers in connection with the glass fiber forming steps, the treatments to form the reaction product on the glass fiber surfaces may be carried out with glass fibers which have alreadyon staple glass fibers by wetting the glass fibers first with been formed, with or without the removal of the original;- size applied to the glass fiber surfaces, such as previousl'y described. Similarly the reaction products may be formed-** soluble oxide or hydroxide to react with the metal salt in forming the insoluble polyvalent metal hydroxide or other reaction product.

It is preferred also to make use of a salt of a polyvalent metal which tends to form a gelatinous type of water insoluble hydroxide such as the salts of aluminum, tin, and zirconium. It is best to make use of the polyvalent metal salts as the chloride or iodide or phosphates but the water soluble acetates, formates and the like may also be used if desired. Though the results are not equivalent, water soluble salts of the bivalent metals such as of lead, copper, and magnesium or the like, may be used either as the chlorides or iodides but preferably as the acetates, formates, or phosphates.

Because of the simplicity in use and because of the ability to eliminate excess by vaporization, it is preferred to make use of ammonium hydroxide as the component for reaction with the polyvalent metal to form the desired reaction product in situ on the glass fiber surfaces. Instead of ammonium hydroxide other inorganic ammonium basic salts capable of releasing hydroxyl groups in solution may be used. Similarly other organic amine bases may be used such as morpholine, triethanolamine, diethanolamine or other volatilizable organic base amine compounds. While it is possible to achieve formation of the desired reaction products with other water soluble oxides or hydroxides, use cannot be made of the sodium, potassium or lithium hydroxides on the glass fiber surfaces.

The concentrations of the solutions applied for reaction on the glass fiber surfaces is not critical as long as the reaction product on the glass fiber surfaces is present in amounts ranging from about $6 to about 10 percent by weight based on the glass fibers. For this purpose, solutions may be used containing the metal salt in concentrations ranging from 16 to 10 percent by weight. The ammonium hydroxide or equivalent material can be provided in concentrations of A to 10 percent by weight, and preferably in concentrations within the range of l6-3 percent by weight. In the alternative, the insolubilizing agent may be suppliedin the form of a vapor of ammonia or other base amine, as by passing the fiber wet with a solution of the polyvalent metal through a chamber in which ammonia is vaporized.

When, for example, glass fibers are coated first with a 2 percent by weight solution of aluminum chloride (AlCl3.6H2O) and subsequently coated while wet with a 0.5 percent solution of ammonium hydroxide, a coating of the desired reaction product in amounts of about 1.27 percent by weight is formed on the glass fiber surfaces. A 4 percent solution of alumninum chloride gives a coating amounting to 2.25 percent by weight when the glass fibers are wet with a 0.5 percent solution of ammonium hydroxide and about a 3.5 percent pickup when wet with a 2.5 percent solution of ammonium hydroxide and about a 3.5 percent pickup when wet with an 8.5 percent solu tion of ammonium hydroxide.

Example 5 Continuous glass fibers sized with a composition of Example 2 are wet with a 4 percent solution of aluminum chloride. While still wet, the fibers are passed through a bath containing a 4 percent solution of ammonium hydroxide and then air dried. When out to 1 inch lengths and incorporated in amounts of about 3 percent by weight with 10 percent by weight asbestos into a Portland cement slurry and then molded under 1000 pounds per square inch pressure, a product having a flexure strength of 4000 pounds per square inch is secured. This is about three to four times greater than the strength secured in the absence of a coating of the reaction product formed in situ on the glass fiber surfaces and over four times greater than a similar cementitious product molded under similar pressure but without pretreatment of the glass fibers.

the water soluble polyv lent m l lt nd he with lb? 15 Asbestos is usually incorporated with the glass fibers in compositions of the type described to permit the distribution of glass fibers in the cement slurry without balling, as described in the copending application Ser. No. 263,998, filed December 28, 1951, now U. S. Patent No. 2,738,285. The amount of asbestos and the need for asbestos depends greatly upon the flexibility or limpness of the glass fibers. When less than 3 percent glass fibers are incorporated as a reinforcement, little, if any, asbestos is used. When present in amounts greater than 3 percent and up to -12 percent, ordinarily 10 percent or more of asbestos is used.

While excellent results have been secured with combinations of the glass fibers treated in the manner described and Portland cement, the reaction products formed on the glass fiber surfaces in accordance with the practice of this invention provides an improved bonding relation and cushioning effect when used in combination with other cementitious materials of the type gypsum, magncsium-oxychloride, magnesium-oxysulphate, and the like.

It will be understood that other changes may be made with respect to the formulations, methods of application and treatment, without departing from the spirit of the invention, especially as defined in the following claims.

What is claimed is:

1. A pressure molded product of an inorganic cement comprising a cured inorganic cement as a continuous phase, glass fibers dispersed throughout the cement phase as a reinforcement and a coating on the glass fiber surfaces in the form of a water insoluble product of the reaction of a salt of a polyvalent metal in solution and a water soluble compound other than an alkali metal base capable of releasing hydroxy groups for reaction in situ on the glass fiber surfaces. 2. A pressure molded product of an inorganic cement comprising a matrix of a cured inorganic cement, glass fibers dispersed throughout the matrix of the cured cement as a reinforcement and a coating on the surfaces of the glass fibers in the form of a water insoluble product which is formed in situ on the glass fiber surfaces by reaction of a salt of a polyvalent metal in solution and a base other than an alkali metal base capable of releasing hydroxy groups and which functions as an anchoring and a protective agent.

3. A pressure molded product of an inorganic cement comprising a matrix of a cured inorganic cement, glass fibers dispersed throughout the matrix of the cured cement as a reinforcement and a coating on the surfaces of the glass fibers in the form of a water insoluble polyvalent metal hydroxide.

4. A cement composition comprising a matrix of a cured inorganic cement, glass fibers dispersed throughout the matrix of the cured cement as a reinforcement and a coating on the surfaces of the glass fibers in the form of a water insoluble coating formed in situ on the glass fiber surfaces by the reaction of a salt of a polyvalent metal in solution and a hydroxy group made available in an ionized state from a base other than an alkali metal base for reaction with the polyvalent metal to form the water insoluble reaction product.

5. A cement composition comprising a matrix of a cured inorganic cement, glass fibers dispersed throughout the matrix of the cured cement as a reinforcement and a coating on the surfaces of the glass fibers in the form of a water insoluble coating formed in situ on the glass fiber surfaces by reaction of a salt of a polyvalent metal in solution and ammonium hydroxide.

6. A cement composition comprising a matrix of a cured inorganic cement, glass fibers dispersed throughout the matrix of the cured cement as a reinforcement and a coating on the surfaces of the glass fibers in the form of a water insoluble polyvalent metal hydroxide coating on the glass fiber surfaces to increase the bonding relation between the glass fiber surfaces and the cement particles.

7. In the method of treating glass fibers for use in combination to reinforce an inorganic cement product wherein the glass fibers are incorporated into a cement slurry and then molded while the inorganic cement is advanced to a cured stage, the improvement which comprises coating the glass fibers prior to combination with the inorganic cement by wetting the surfaces of the glass fibers with an aqueous solution of a water soluble salt of a polyvalent metal, introducing hydroxy ions from a base other than an alkali metal base onto the fibers wet with the solution of the salt of the polyvalent metal for reaction in situ on the glass fiber surfaces to form a water insoluble reaction product which protects the fibers and increases the bonding relation between the glass fiber surfaces and the inorganic cement.

8. In the method of manufacturing a reinforced molded product of inorganic cement wherein the glass fibers are incorporated as a reinforcement into the cement slurry and which is molded while the cement material is advanced to a cured stage, the improvement comprising coating the glass fibers prior to combination with the inorganic cement by wetting the surfaces of the glass fibers with an aqueous solution of a water soluble salt of a polyvalent metal capable of forming gelatinous hydroxides, treating the surfaces of the fibers wet with the solution of the salt of the polyvalent metal with a material other than an alkali metal base capable of releasing hydroxy ions for reaction in situ on the glass fiber sur faces to form a water insoluble reaction product which protects the fibers and increases the bonding relation between the glass fiber surfaces and the inorganic cement.

9. In the method of manufacturing a reinforced molded product of inorganic cement wherein glass fibers are incorporated as a reinforcement into a cement slurry and which is molded while the cement material is advanced to a cured stage, the improvement comprising coating the glass fibers prior to combination with the inorganic cement by wetting the surfaces of the glass fibers with an aqueous solution of a water soluble salt of a polyvalent metal, applying a solution of ammonium hydroxide to the wet surfaces of the glass fibers for reaction in situ on the glass fiber surfaces to form a water insoluble reaction product, and then drying the coating on the glass fiber surfaces.

References Cited in the file of this patent UNITED STATES PATENTS 2,085,129 Stowener June 29, 1937 2,246,537 Rembert June 24, 1941 2,315,892 Booth Apr. 6, 1943 2,323,387 Edelstein July 6, 1943 2,361,830 Edelstein Oct. 31, 1944 2,373,914 Quinn Apr. 17, 1945 2,392,805 Biefeld Ian. 15, 1946 2,425,883 Jackson Aug. 19, 1947 2,451,805 Callinan Oct. 19, 1948 2,511,472 Kmecik June 13, 1950 2,531,571 Hyde Nov. 28, 1950 2,610,957 Steinman et al Sept. 16, 1952 2,661,288 Barbaras Dec. 1, 1953 2,671,744 Biefeld Mar. 9, 1954 

1. A PRSSURE MOLDED PRODUCT OF AN INORGANIC CEMENT COMPRISING A CURED INORGANIC CEMENT AS A CONTINUOUS PHASE, GLASS FIBERS DISPERSED THROUGHOUT THE CEMENT PHASE AS A REINFORCEMENT AND A COATING ON THE GLASS FIBER SURFACES IN THE FORM OF A WATER INSOLUBLE PRODUCT OF THE REACTION OF A SALT OF A POLYVALENT MEAL IN SOLUTION AND A WATER SOLUBLE COMPOUND OTHER THAN AN ALKALI METAL BASE CAPABLE OF RELEASING HYDROXY GROUPS FOR REACTION IN SITU ON THE GLASS FIBER SURFACES.
 7. IN THE METHOD OF TREATING GLASS FIBERS FOR USE IN COMBINATION TO REINFORCE AN INORGANIC CEMENT PRODUCT WHEREIN THE GLASS FIBERS AR INCORPORATED INTO A CEMENT SLURRY AND THEN MOLDED WHILE THE INORGANIC CEMENT IS ADVANCED TO A CURED STAGE, THE IMPROVEMENT WHICH COMPRISES COATING THE GLASS FIBERS PRIOR TO COMBINATION WITH THE INORGANIC CEMENT BY WETTING THE SURFACES OF THE GLASS FIBERS WITH AN AQUEOUS SOLUTION OF A WATER SOLUBLE SALT OF A POLYVALENT METAL, INTRODUCING HYDROXY IONS FROM A BASE OTHER THAN AN ALKALI METAL BASE ONTO THE FIBERS WET WITH THE SOLUTION OF THE SALT OF THE POLYVALENT METAL FOR REACTION IN SITU ON THE GLASS FIBER SURFACES TO FORM A WATER INSOLUBLE REACTION PRODUCT WHICH PROTECTS THE FIBER AND INCREASES THE BONDING RELATION BETWEEN THE GLASS FIBER SURFACES AND INORGANIC CEMENT. 